Branched polyorganosiloxane polymers

ABSTRACT

Hydrophilic polyquaternary polyorganosiloxane copolymers and their use as wash-resistant hydrophilic softeners.

This is a 371 of PCT/EP03/02861 filed 19 Mar. 2003 (international filingdate).

The present invention relates to branched polyorganosiloxane polymers, aprocess for their production, their use, and compositions containingthem. The invention relates in particular to hydrophilic polyquaternarypolyorganosiloxane copolymers and their use in particular aswash-resistant hydrophilic softeners.

BACKGROUND OF THE INVENTION

Polysiloxanes containing amino groups are known as textile softeners (EP441530). The introduction of amino structures modified by ethyleneoxide/propylene oxide units as side chains causes an improvement of theeffect (U.S. Pat. No. 5,591,880, U.S. Pat. No. 5,650,529). The alkyleneoxide units permit in this case the selective setting of thehydrophilic-hydrophobic balance. Disadvantageous from the syntheticstandpoint is the fact that, included in the synthesis strategy, thereis the difficult esterification of amino alcohols with siloxane-boundcarboxylic acid groups and, with respect to the softening properties,the general comb structure of the products.

To eliminate these disadvantage is has been proposed to convertα,ω-epoxymodified siloxanes with α,ω-aminofunctionalized alkylene oxidesand to use these products as hydrophilic softeners (U.S. Pat. No.5,807,956, U.S. Pat. No. 5,981,681).

To improve the substantivity, experiments were undertaken to introducequaternary ammonium groups in alkylene oxide-modified siloxanes.

Branched alkylene oxide-modified polysiloxane quats have beensynthesized from α,ω-OH terminated polysiloxanes and trialkoxysilanes bycondensation. The quaternary ammonium structure is introduced via thesilane, where the quaternary nitrogen atom is substituted with alkyleneoxide units (U.S. Pat. No. 5,602,224).

Severe comb-like alkylene oxide-modified polysiloxane quats have alsobeen described (U.S. Pat. No. 5,098,979). The hydroxyl groups ofcomb-like substituted polyether siloxanes are converted withepichlorohydrine into the corresponding chlorohydrine derivatives.Subsequently a quaternization is done with tertiary amines.

For this reason, the hydroxyl groups of comb-like substituted polyethersiloxanes have been esterified alternatively with chloroacetic acid.Through the carbonyl activation the concluding quaternization can becompleted in a simplified manner (U.S. Pat. No. 5,153,294, U.S. Pat. No.5,166,297).

In U.S. Pat. No. 6,242,554 the α,ω-difunctional siloxane derivatives aredescribed that each have a separate quaternary ammonium and alkyleneoxide unit. These materials are distinguished by an improvedcompatibility with polar environments.

The reaction of α,ω-diepoxides with tertiary amines in the presence ofacids provides α,ω-diquaternary siloxanes which can be used for thepurposes of hair-grooming (DE-PS 3 719 086). Along withtetraalkyl-substituted quaternary ammonium structures, aromaticimidazolinium derivatives are also claimed.

A reduction of the ability to be washed out of the hair can be achievedif the α,ω-diepoxides are converted with ditertiary amines in thepresence of acids into long-chain polyquaternary polysiloxanes (EP282720).

Aromatic quaternary ammonium structures are not disclosed. Derivativesof this type are treated in U.S. Pat. No. 6,240,929. In a first step twodiamines having two imidazole units are synthesized from imidazole andsuitable difunctional alkylation agents, said diamines subsequentlybeing converted into polyquaternary polysiloxanes in a manner analogousto EP 282720. Cationic compounds produced in this way should have afurther increased compatibility with respect to the anionic surfactantspresent in cosmetic formulations. However, the resistance to beingwashed out of the hair relates to short-term attack of primarily waterand very mild surfactants not irritating the skin while wash-resistant,hydrophilic softeners for textiles have to withstand the attack ofconcentrated surfactant solutions with high fat-dissolving anddirt-dissolving power. Making it more difficult in addition is the factthat modern detergents contain strongly alkaline complex promoters,oxidatively acting bleaches, and complex enzyme systems, with the fibersoften being exposed to the action for hours at elevated temperatures.

Alternative approaches to the improvement of the compatibility withanionic surfactant systems or the efficiency of the siloxane depositionon surfaces are targeted at the use of greater amounts of cationicsurfactants (WO 00-71806 and WO 00-71807) or the utilization of cationicpolysaccharide derivatives (J. V. Gruber et al., Colloids and SurfacesB; Biointerfaces 19 (2000), 127-135) in mixtures with polydimethylsiloxanes.

Highly charged, very hydrophilic synthetic polycationics are also in theposition to improve the compatibility with anionic surfactant systems(U.S. Pat. No. 6,211,139) or in the presence of solutions of anionicsurfactants to associate with fibers (WO 99-14300). In the latterdocument, polyimidazolinium derivatives, among others, are described.

None of the proposals treated represents a satisfactory solution to theproblem of obtaining the soft feel possible through silicone and thepronounced hydrophily after initial finishing of a textile material evenwhen it is exposed to attack of aggressive detergent formulations, thatis, among others, detergent formulations with a high pH value (>10) andhighly active surfactants in the course of repeated washing processesat, in given cases, an elevated temperature.

A fundamentally different approach is described in DE-OS 3 236 466. Theconversion of OH-terminated siloxanes with alkoxysilanes containingquaternary ammonium structures provides reactive intermediate productswhich are supposed to be cross-linked with suitable cross-linkingagents, such as trialkoxysilanes, on the fiber surface to formwash-resistant layers. A decisive disadvantage of this approach is thefact that the necessary hours-long stability of an aqueous finishingbath cannot be guaranteed and unforeseen cross-linking reactions in thebatch can already occur before the textile finishing.

Self-cross-linking emulsions of aminosiloxanes are also known (U.S. Pat.No. 4,661,577). For this, trialkoxysilyl structures terminal in themolecule are introduced.

A cross-linking of aminosiloxanes can also be achieved by reaction withepichlorohydrine or diepoxides (WO 01-27232) or, analogous to Michaeladdition, by a reaction with diacrylates (DE 198 03 468).

Alternative approaches with the participation of cross-linked structuresdeal with, among other things, mixtures of hydrocarbon-based quats(compounds containing quaternary ammonium groups) and cross-linkedsiloxanes (U.S. Pat. No. 4,908,140) or the additional incorporation ofstraight-chain siloxanes (U.S. Pat. No. 4,978,462).

WO 02-10257 describes linear polysiloxane compounds which containpolyalkylene oxide structural units, ammonium groups, and polysiloxanestructural units in which the possibility of a branching is in factmentioned but no branched polysiloxane compounds or actual branchingcomponents needed to build them are described. The mentionedmulti-functional groups thus do not serve for building branches butrather the saturation within the linear main chain or for buildingmonofunctional side chains.

These linear polysiloxane compounds, however, still always havedisadvantages with regard to their substantivity.

Branched polysiloxane compounds were previously considered by thoseskilled in the art as unsuitable to serve as soluble or emulsifiable,i.e., applicable, softeners because they incline toward-the formation ofhighly molecular gels so that they cannot be applied to the fibers fromaqueous solution.

It was thus completely surprising that the special, branchedpolysiloxane polymers, as they were prepared for the first time by theinventors of the present patent application, were, on the one hand,soluble and applicable and have, at the same time, a highersubstantivity (durability), and even in many cases an increasedsoftening action, with respect to the linear polysiloxane compounds.

The hydrophilic, polyquaternary polysiloxane copolymers according to theinvention can thus lend textiles, after appropriate application, a softfeel typical of silicone and a pronounced hydrophilicity, and thisprofile of properties is also not lost after the action of detergentformulations during repeated washing processes at, in given cases, anelevated temperature.

Furthermore, the hydrophilic, polyquaternary polysiloxane copolymersaccording to the invention can serve as separate softeners or assofteners in formulations for washing fibers and textiles which arebased on non-ionogenic or anionic/non-ionogenic surfactants as well asan aid to ironing and means for preventing or reversing creases intextiles.

SUMMARY OF THE INVENTION

The present invention thus provides branched polyorganosiloxane polymerscontaining

-   -   at least one group of the structure

-   -   at least one group of the structure

-   -   at least one group of the structure

-   -   as well as at least one branching unit which is chosen from the        group which consists of S^(v) and V^(v),        where    -   Groups V are connected to groups Q and S,    -   Groups Q are not connected to groups S    -   the groups S, S^(v), V, V^(v), and Q in a polymer molecule can        be the same or different and where

where

-   -   R¹ can be the same or different and is chosen from the group        which consists of: C₁ to C₂₂ alkyl, fluoro(C₁-C₁₀)alkyl and        C₆-C₁₀ aryl, n =0 to 1000    -   S^(v) is a three or higher valent organopolysiloxane unit,    -   Q is a divalent organic group containing at least one ammonium        group,    -   V represents a divalent, straight-chain, cyclic or branched,        saturated, unsaturated, or aromatic hydrocarbon group with up to        1,000 carbon atoms which, in given cases, can contain one or        more groups        -   chosen from chosen from —O—, —NH—, —NR¹—, where R¹ is            defined as above,

—C(O)—, and —C(S)—, and which, in given cases, can be substituted withone or more hydroxyl groups,

-   -   V^(v) represents a trivalent or higher valent, straight-chain,        cyclic or branched, saturated, unsaturated, or aromatic        hydrocarbon group with up to 1,000 carbon atoms which, in given        cases, can contain one or more groups chosen from —O—, —NH—,        —NR¹—, wherein R¹ is defined        as above,

—C(O)—, and —C(S)—, and which, in given cases, can be substituted withone or more hydroxyl groups,and where the positive charges resulting from the ammonium group areneutralized by organic or inorganic acid anions and their acid additionsalts.

DETAILED DESCRIPTION

In a preferred form of embodiment the divalent organic group Qcontaining at least one ammonium group is chosen from the group whichconsists of

a quaternized imidazole unit of the structure

a quaternized pyrazole unit of the structure

where R⁵, R⁶, and R⁷ can be the same of different and are chosen fromthe group which consists of: H, halogen, hydroxyl group, nitro group,cyano group, thiol group, carboxyl group, alkyl group, monohydroxyalkylgroup, polyhydroxylalkyl group, thioalkyl group, cyanoalkyl group,alkoxy group, acyl group, acetyloxy group, cycloalkyl group, aryl group,alkylaryl group, and groups of the type —NHR^(w) in which R^(w) means H,alkyl group, monohydroxyalkyl group, polyhydroxyalkyl group, acetylgroup, ureido group, and the groups R⁶ and R⁷ with the carbon atomsbinding them to the imidazole ring, or two of the groups R⁵, R⁶, and R⁷with the carbon atoms binding them to the pyrazole ring, can formaromatic five-element to seven-element rings, more preferably R⁵, R⁶,and R⁷ are the same or different and are chosen from the group whichconsists of: H and C₁-C₆ alkyl, and the groups R⁶ and R⁷ with the carbonatoms binding them to the imidazole ring, or two of the groups R⁵, R⁶,and R⁷ with the carbon atoms binding them to the pyrazole ring, can forma phenyl ring.a diquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a diquaternized unit of the structure

a monoquaternized unit of the structure

a monoquaternized unit of the structure

a diquaternized unit of the structure

a monoquaternized unit of the structure

a monoquaternized unit of the structure

where

t=2 to 10 and R²═H or represents a monovalent, straight-chain, cyclic orbranched, saturated, unsaturated, or aromatic hydrocarbon group with upto 40 carbon atoms which can contain one or more groups chosen from —O—,—NH—, —C(O)—, and —C(S)—, and which, in given cases, can be substitutedwith one or more hydroxyl groups,

R² preferably represents a monovalent or divalent, straight-chain,cyclic or branched, saturated, unsaturated, or aromatic hydrocarbongroup with up to 30 carbon atoms (for non-aromatic hydrocarbon groupswith 1 to 30 carbon atoms) which can contain one or more groups chosenfrom —O—, —NH—, —C(O)—, and —C(S)—, and which, in given cases, can besubstituted with one or more hydroxyl groups,

Still more preferably R²=

with R⁴=a straight-chain, cyclic or branched C₁ to C₁₈ hydrocarbon groupwhich can contain one or more groups chosen from —O—, —NH—, —C(O)—, and—C(S)—, and which can be substituted with one or more hydroxyl groups,especially unsubstituted C₅ to C₁₇ hydrocarbon groups which are derivedfrom the corresponding fatty acids or hydroxylated C₃ to C₁₇ groupswhich can be traced back to hydroxylated carboxylic acids, especiallysaccharide carboxylic acids, and quite especially mean

R³ can have the meaning of R², where R² and R³ can be the same ordifferent or R² and R³ together with the positively charged nitrogenatom form a five- to seven-element heterocycle which, in given cases,can have in addition one or more nitrogen, oxygen, and/or sulfur atoms,

R⁸ has the meaning of R², where R⁸ and R² can be the same or different.

In an additional preferred form of embodiment of the branchedpolyorganosiloxane polymers according to the invention S is a group ofthe structure:

wherein R¹ is chosen from the group which consists of methyl, ethyl,trifluoropropyl, and phenyl and n is from 0 to 500, more preferably 0 to350, particularly preferably 0 to 160 and 160 to 350, quite particularlypreferably 0 to 110 and 200 to 350, specifically preferably 0 to 80,quite specifically preferably 0 to 50.

In an additional preferred form of embodiment of the branchedpolyorganosiloxane polymers according to the invention V represents adivalent, straight-chain, cyclic or branched, saturated, unsaturated, oraromatic hydrocarbon group with up to 400 carbon atoms which can containone or more groups chosen from —O—, —NH—, —NR¹—, where R¹ is defined asabove,

—C(O)—, and —C(S)—, and can be substituted with one or more hydroxylgroups.

The combination of groups

is done in the branched polyorganosiloxane polymers according to theinvention so that the groups V (V and V^(v)) are connected to the groupsQ or S(S and S^(v)) but the groups Q are not connected to the groups (Sand S^(v)). Moreover, all the combinations of said groups are possiblewhere, according to production, block-like and/or static copolymers canresult.

Thus, for example, block-like sequences of -(S-V) units or -(Q-V) unitscan be present. In a preferred form of embodiment of the branchedpolyorganosiloxane polymers according to the invention they containrepeating units of the structure

where Q and S are defined as above, V¹ and V² have the meaning of V butare different from one another along with said branching units (S^(v),V^(1v) or V^(2v)). Preferably, the branched polyorganosiloxane polymersaccording to the invention have repeating units of the structure

where Q, V¹, V², and S are defined as above along with said branchingunits.

In an additional preferred form of embodiment of the branchedpolyorganosiloxane polymers according to the invention they containrepeating units of the structure

where Q is defined as above, and —V¹— is chosen from groups of thestructures:

-   -   —R⁹— where R⁹ represents a divalent, saturated or simply or        multiply unsaturated, straight-chain or branched, hydrocarbon        group with two to 25 carbon atoms such as    -   —(CH₂)_(u)C(O)O—[(CH₂CH₂O)_(q)—(CH₂CH(CH₃)O)_(r)]—C(O)(CH₂)_(u)—    -   —(CH₂)_(u)C(O)O—R⁹—O—C(O)(CH₂)_(u)—, where R⁹ is defined as        previously,    -   —(CH₂)_(u)—R¹⁰—(CH₂)_(u)—, where R¹⁰ is an aromatic group,    -   —[CH₂CH₂O]_(q)[CH₂CH(CH₃)O]_(r)—CH₂CH₂—,    -   —CH(CH₃)CH₂O[CH₂CH₂O]_(q)[CH₂CH(CH₃)O]_(r)CH₂CH(CH₃)    -   —CH₂CH(OH)CH₂—,    -   —CH₂CH(OH)(CH₂)₂CH(OH)CH₂—,    -   —CH₂CH(OH)CH₂OCH₂CH(OH)CH₂OCH₂CH(OH)CH₂— and    -   CH₂CH(OH)CH₂O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)CH₂CH(OH)CH₂—        where    -   u is from 1 to 3,    -   q and r are from 0 to 200, preferably from 0 to 100, more        preferably from 0 to 70, and particularly    -   preferably 0 to 40, and    -   q+r>0.    -   Preferred variants of V¹ are structures of the formula        —CH₂C(O)O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—C(O)CH₂—,        —CH₂CH₂C(O)O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—C(O)CH₂CH₂—,        —CH₂CH₂CH₂C(O)O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—C(O)CH₂        esterified alkylene, alkenylene, alkinylene units, especially of        the formulas        —CH₂C(O)O—[CH₂]_(o)—OC(O)CH₂—,        —CH₂CH₂C(O)O—[CH₂]_(o)—OC(O)CH₂CH₂—,        —CH₂CH₂CH₂C(O)O—[CH₂]_(o)—OC(O)CH₂CH₂CH₂—        —CH₂C(O)O—CH₂C≡CCH₂—OC(O)CH₂—,        —CH₂Ch₂C(O)O—CH₂C≡CCH₂—OC(O)CH₂CH₂—,        —Ch₂CH₂CH₂C(O)O—CH₂C≡CCH₂—OC(O)CH₂CH₂CH₂—,        —CH₂C(O)O—Ch₂CH═CHCH₂—OC(O)CH₂—,        —CH₂CH₂C(O)O—CH₂CH═CHCH₂—OC(O)CH₂CH₂—,        —CH₂CH₂CH₂C(O)O—CH₂CH═CHCH₂—OC(O)CH₂CH₂CH₂—,        alkylene, alkenylene, alkinylene, and aryl units, especially of        the structure        —[CH₂]_(o)—        with o=2 to 6        —CH₂C≡CCH₂—, —CH₂CH═CHCH₂—, —CH(CH₃)CH₂CH₂—,

polyalkylene oxide units, especially of the formulas—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—CH₂CH₂—,—CH(CH₃)CH₂O[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—CH₂CH(CH₃)—with monohydroxyfunctional units, dihydroxyfunctional units, orpolyhydroxyfunctional units, especially of the formulas—CH₂CH(OH)CH₂—, —CH₂CH(OH)(CH₂)₂CH(OH)CH₂—,—CH₂CH(OH)CH₂OCH₂CH(OH)CH₂OCH₂CH(OH)CH₂—,—CH₂CH(OH)CH₂O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—CH₂CH(OH)CH₂—withq=0 to 200r=0 to 200

Preferably q=1 to 50, in particular 2 to 50, especially 1 to 20, quiteespecially 1 to 10, as well as 1 or 2, r=0 to 100, in particular 0 to50, especially 0 to 20, quite especially 0 to 10, as well as 0 or 1 or2.

In an additional preferred form of embodiment of the branchedpolyorganosiloxane polymers according to the invention they containrepeating units of the structure

where invention V² is a divalent, straight-chain, cyclic or branched,saturated, unsaturated, or aromatic C₂ to C₁₆ hydrocarbon group whichcan contain one or more groups chosen from —O—, —NH—, —NR¹—,where R¹ is defined as above,

—C(O)—, and —C(S)—, and can be substituted with one or more hydroxylgroups. Still more preferably —V²— is chosen from groups of thestructures:

—(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅—, —(CH₂)₆—,—CH═CHCH₂—, —CH═CHCH₂CH₂—,—CH₂CH₂CH₂OC(O)CH₂—, —CH₂CH₂CH₂OC(O)CH₂CH₂—,—CH═CHCH₂OC(O)CH₂— and —CH═CHCH₂OC(O)CH₂CH₂—.

with v+w≧0.

In a preferred form of embodiment of the invention, the branchedpolyorganosiloxane polymer has a branching unit S^(v) which is atrivalent or higher valent organopolysiloxane group which has at leastthree silicon atoms which are each connected to three or more groups Vor V^(v) via a bond to a carbon atom of the respective group V or V^(v).

The group S^(v) has, in addition to the group S, more of the followingsiloxy units which make it possible to link 3 and more bonds to V² orV^(2v). S^(v) includes: equilibration and condensation products, thefollowing methylsiloxane units contain: M, D, T, and Q (W. Noll, Chemieund Technologie der Silicone, [=Chemistry and Technology of Silicones],VCH, Weinheim, 1968) as well as units M′, D′, and T′ which are derivedfrom M-, D-, and T-units in which formally by omission of a methyl groupa free valence is formed which bonds to V.

Examples of the S^(v) groups include, for example, at least trivalentorganopolysiloxane groups of the structure:

with n¹≧1 (S^(v)I) for (S^(v)I): with n²≧3

The molar percentage of the bonds in S^(v) to V² or V², is 0.002 to 50%,preferably 0.01 to 30%, especially preferably 0.1 to 20%.

In an additional preferred form of embodiment of the invention, thebranched polyorganosiloxane polymers have a branching group of theformulaV^(1v)(-Q-)_(x)where V^(1v)(-Q-)_(x) is a trivalent or higher valent group, Q isdefined as above, and x is a whole number of at least three, and whereV^(1v) is chosen from the group which consists of:R¹¹—[(CH₂CH₂O)_(v)(CH₂CH(CH₃)O)_(w)—CO—(CH₂)_(u)]₃₋₆—, where

-   -   R¹¹ is a trivalent or hexavalent group which is derived from a        polyol in which 3 to 6 hydroxyl-hydrogen atoms are substituted,    -   v and w are from 0 to 200,    -   v+w≧0, and    -   u=1 to 3        R¹¹—[(CH₂CH₂O)_(v)(CH₂CH(CH₃)O)_(w)—CH₂CH(OH)CH₂]₃₋₆—, where    -   R¹¹, v, and w are defined as above

where t is from 2 to 10 and R² is defined as above, preferably H ormethyl,

where t is from 2 to 10 and V³ is a partial structure which is derivedfrom V or V^(v), and,

where t is from 2 to 10 and R² and V³ are defined as above, R² ispreferably H or methyl.

The aforementioned polyol is preferably chosen from the group whichconsists of: glycerol, trimethylolpropane, pentaerythritol, sorbitol,and sorbitan. Examples for V^(1v) include: trivalent and higher valentstructures of based on esters of polyols with C₂ to C₆ carboxylic acidgroups or ethers of beta-hydroxyalkyl groups, proceeding from theconversion of polyols with oxirans, such as epichlorohydrine,vinylcyclohexene monoepoxide, vinylcyclohexene diepoxide.

Along with this, various ones of these groups can form the group V^(1v)on the polyol.

Preferred polyols are glycerol, trimethylolpropane, pentaerythritol,sorbitol, and sorbitan, which can be esterified with chloroacetic acidor chloropropionic acid.

with v+w≧0

The molar percentage of V^(1v) in V¹ is 0.002 to 50%, preferably 0.01 to30%, especially preferably 0.1 to 20%.

In addition, a part of the Q groups binds to V^(2v). These are, forexample, trivalent and higher valent structures of V^(2v), based onesters of polyols with C₂ to C₆ carboxylic acid groups or ethers ofbeta-hydroxyalkyl groups, proceeding from the conversion of polyols withoxirans, such as epichlorohydrine, vinylcyclohexene monoepoxide,vinylcyclohexene diepoxide.

Along with this, various ones of these groups can form on the polyol,together with it, the group V^(2v). In analogy thereto, the group S^(v)can be linked to different groups V² or V^(2v).

The units V² and S^(v) are defined as above under V² and can be linkedto S^(v) in this form of embodiment in such a manner that different V²groups bind to an S^(v). Likewise, different groups V^(2v) and a groupS^(v) can be bound.

In an additional form of embodiment of the invention, the branchedpolyorganosiloxane polymers S^(v) can be bound to a branching group ofthe structure V^(2v) which is connected to at least one group S or S^(v)and where V² is a trivalent or higher valent group which is chosen fromthe group which consists of:-(Z-)_(y)R¹²[—(CH₂CH₂O)_(v)(CH₂CH(CH₃)O)_(w)—CO—(CH₂)_(u)]_(z)—, where

-   -   R¹² is a trivalent or hexavalent group which is derived from a        polyol in which 3 to 6 hydroxyl-hydrogen atoms are substituted,        and    -   Z is a divalent hydrocarbon group with up to 20 carbon atoms        which can contain one or more groups chosen from —O— and —C(O)—,        and which, in given cases, can be substituted with one or more        hydroxyl groups, and where the group Z is bonded by one of its        carbon atoms to a silicon atom of the groups S or S^(v),    -   v and ware from 0 to 200,    -   v+w≧0,    -   u=1 to 3,    -   y=1 to 6, preferably 1,    -   z=0 to 5, preferably 2 to 5, and    -   z+y=3 to 6, preferably 3,        (—)_(m)R [—O(CH₂CH₂O)_(v)(CH₂CH(CH₃)O)_(w)—CO—CH₂)_(u)]_(n)—,        where    -   R¹³ is a trivalent or hexavalent, saturated or unsaturated,        linear, branched or cyclic hydrocarbon group with up to 10        carbon atoms,    -   (—) represents a single bond to a silicon atom of the group S or        S^(v),    -   v and w are from 0 to 200,    -   v+w≧0,    -   u=1 to 3,    -   m 1 or 2, preferably 1,    -   n=1 to 5, preferably 2 to 5, and    -   m+n=3 to 6, preferably 3,        (—)_(m)R¹³[—O(CH₂CH₂O)_(v)(CH₂CH(CH₃)O)_(w)—CH₂CH(OH)CH₂]_(n)—,        where    -   m, R¹³, v, w, and n are defined as above,        —(Z—)_(y)R¹²[—(CH₂CH₂O)_(v)(CH₂CH(CH₃)O)_(w)—CH₂CH(OH)CH₂]_(z)—,        where    -   Z, y, R¹², v, w, and z are defined as above.

Examples of the groups V^(2v) include:

with v+w≧0.The molar percentage of V^(2v) in V² is 0.002 to 50%, preferably 0.01 to30%, especially preferably 0.1 to 20%.

In a preferred form of embodiment of the branched polyorganosiloxanepolymers, the molar ratio of the sum of the branching units S^(v) andV^(v) to the sum of the linear repeating units S, V, and Q is 0.001 to20%.

In an additional preferred form of embodiment, the branchedpolyorganosiloxane polymers contain the branching units V^(v) and S^(v),where the molar ratio of V^(v) to V is preferably from 0.002% to 20% andthe molar ratio of S^(v) to S is preferably from 0.002 to 20%.

In order to avoid the formation of gel-like branched polyorganosiloxanepolymers which are not completely soluble, the amount of the branchingunits is, in accordance with this aim, limited from above.

An additional limiting of the molecular weight is caused by the finalshortstopping arising in the reaction between epoxides and water oralcohol, or alternatively by the additional use of trialkylamines.

That means the branched polyorganosiloxane polymers can also have, alongwith the terminal groups resulting naturally from the conversion of themonomeric starting materials, monofunctional chain termination agentssuch as trialkylamines, etc., and, for example, ammonium, ether, orhydroxy-terminal groups resulting therefrom. Moreover, the molecularweight can be limited via the selection and stochiometry of the units S,V, and Q.

The branched polyorganosiloxane polymers according to the inventionfurthermore contain organic or inorganic acid anions for theneutralization of the positive charges resulting from the ammoniumgroups. Moreover, amino groups present can be converted by the additionof inorganic or organic acids into the corresponding acid addition saltswhich also are a part of the object of the invention. Organic orinorganic acid groups are groups which result formally from theelimination of one or more protons from organic or inorganic acids andinclude, for example, halide ions, especially chloride and bromide,alkylsulfates, especially methosulfate, carboxylates, especiallyacetate, propionate, octanoate, decanoate, dodecanoate, tetradecanoate,hexadecanoate, octadecanoate, oleate, sulfonates, especially toluenesulfonate. However, other anions can also be introduced by ion exchange.To be named are, for example, organic anions such as polyethercarboxylates and polyether sulfates. Preferred are, for example, saltsof fatty acids and chloride. The organic or inorganic anionic acidgroups can be the same or different from one another in the branchedpolyorganosiloxane polymers according to the invention.

The invention relates furthermore to a process for the production of thebranched polyorganosiloxane polymers which includes the conversion of:

-   a) at least one organic compound which has two amino groups and    which can contain a polyorganosiloxane group, with-   b) at least one organic compound which has two epoxy groups and    which can contain a polyorganosiloxane group, with-   c) at least one organic compound which has two halogen    alkylcarbonyloxy groups and which can contain a polyorganosiloxane    group, as well as-   d) at least one branching compound which is derived from one of the    organic compounds a), b), and/or c) in such a manner that they each    have at least one additional amine, epoxy, or chloroalkylcarbonyloxy    functionality    with the specification that at least one of the compounds a) to d)    contains a polyorganosiloxane group.

The starting point for the syntheses of the substances according to theinvention are α,ω-Si—H functionalized siloxanes of the general structure

where R¹ and n have the meanings specified above. To the extent thatthey are not available commercially, these siloxanes can be producedaccording to known processes, for example, by acidic equilibration orcondensation (Silicone, Chemie und Technologie [=Silicones, Chemistryand Technology], Vulkan-Verlag, Essen 1989, pp. 82-84).

The hydrogen siloxanes can be converted to the structural elements S—V²and S—V²—Q, for example, on two paths.

On the one hand, it is possible first to bond unsaturated structuresbearing tertiary amino functions, e.g. N,N-dimethylallylamine, byhydrosilylation directly to the hydrogen siloxane in α,ω-position. Thisprocess is generally known (B. Marciniec, Comprehensive Handbook onHydrosilylation, Pergamon Press, Oxford 1992, P. 122-124).

On the other hand it is preferred to first generate by hydrosilylationreactive α,ω-functionalized intermediate products which subsequently canbe converted into α,ω-ditertiary amino structures or directly intoquaternary ammonium structures. Suitable starting substances for thegeneration of reactive intermediate stages are, for example, halogenatedalkenes or alkines, especially allyl chloride, allyl bromide,chloropropine, and chlorobutine, unsaturated halogen carboxylic acidesters, especially chloroacetic acid allyl ester, chloroacetic acidpropargyl ester, 3-chloropropionic acid allyl ester, and,3-chloropropionic acid propargyl ester and epoxyfunctional alkenes, forexample, vinylcyclohexene oxide and allylglycid ether. The generalexecution of hydrosilylations with representatives of said groups ofsubstances is also known (B. Marciniec, Comprehensive Handbook onHydrosilylation, Pergamon Press, Oxford, 1992, pp. 116-121, 127-130,134-137, 151-155).

In a subsequent step, the reactive intermediate stages can then bebrought into reaction with, for example, with compounds bearing primary,secondary, or tertiary amino functions. Suitable representatives areN,N-dialkylamines, for example, dimethylamine, diethylamine,dibutylamine, diethanolamine, and N-methylglucamine, cyclic secondaryamines, for example, morpholine and peperidine, amino amides bearingsecondary amino functions, for example, the conversion products ofdiethylene triamine or dipropylene triamine with lactones such asγ-butyrolactone, gluconic acid-δ-lactone, and glucopyranosyl arabinonicacid lactone (DE-OS 43 18 536, Examples 11a, 12a, 13a) orsecondary-tertiary diamines (amines with secondary and tertiary amineunits) such as, for example, N-methylpiperazine. It is especiallypreferred to utilize corresponding imidazole or pyrazole derivatives,especially imidazole and pyrazole to introduce tertiary amino functions.

As partners for the epoxide derivatives preferably used in one form ofembodiment as a possible reactive component, said secondary-tertiarydiamines are particularly suitable, as are imidazole and pyrazole. Inthis manner, the alkylations can be directed regioselectively andwithout additional expenditure in nitrogen atoms bearing the hydrogenatoms.

To assure a quantitative conversion of the reactive groupings intotertiary amino structures the amines are used in a ratio of 1≦(Σsecondary amino groups:reactive groups)≦10, preferably 1 to 3,especially 1 to 2, particularly especially 1. An amine excess must, ingiven cases, be removed.

The binding of the above-described α,ω-ditertiary aminosiloxanes to aunit —V¹— leads to the formation of Q.

A preliminary preparation of a precondensate -Q-V¹-Q- terminatedessentially by amino groups can, on the other hand, open the possibilityof implementing the copolymer formation directly with suitable reactiveintermediate stages, for example, epoxy derivatives.

It is also preferred to present together, and subsequently to bring toreaction, the reactive intermediate stages and the starting componentsfor building the sequence -Q-V¹-Q-.

Finally, it is possible to dose the reactive intermediate stages inincrements into the presented components for building the sequence-Q-V¹-Q- over a period of time, or, vice versa, to add these componentsin increments to the reactive intermediate stages.

Independent of the choice of one of the reaction paths described aboveand the question closely associated therewith whether amino units firstlimit the siloxane or the precondensate, a total stochiometry should beadhered to with regard to the molar amounts which can be described inessence by Σ (primary+secondary+tertiary N):Σ(reactive groups on thesiloxane+reactive groups on linkers forming V¹)=1:1.

In the scope of the invention, it is possible to deviate from thispreferred total stochiometry. However, products are then obtained whichleave an excess of a non-reacting starting component.

Along with the reaction's total stochiometry treated above, the choiceof the precursors (n) forming the linkers V¹ is of great importance.

Suitable precursors (starting components) are, on the one hand, thehalogen carboxylic acid esters of the alkylene oxides. Preferredstarting materials for their synthesis' are low-molecular, oligomericand polymeric alkylene oxides of the general compositionHO[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)Hwhere q and r have the meanings specified above. Preferredrepresentatives with regard to the alkylene oxide block are ethyleneglycol, diethylene glycol, triethylene glycol, tetraethylene glycol, theoligoethylene glycols with molecular weights of 300 to 1000 g/mol,especially 400, 600, and 800 as well as 1,2-propylene glycol,1,3-propylene glycol, and dipropylene glycol.

The esterificiation of the alkylene oxides is done in a manner known perse (Organikum, Organisch-chemisches Grundpraktikum [=Organikum, BasicPractice of Organic Chemistry], 17th edition, VEB Deutscher Verlag derWissenschaften, Berlin, 1988, pp. 402-408) by reaction with theC₂-halogen carboxylic acids to C₄-halogen carboxylic acids, theiranhydrides, or acid chlorides. Preferably the acid chlorides ofchloroacetic acid and 3-chloropropionic acid are used and the reactioncarried out in the absence of solvents.

In an analogous manner alkane diols, alkene diols, and alkine diols canbe converted into the corresponding reactive ester derivatives.Exemplary alcohols are 1,4-butandiol, 1,6-hexandiol, 1,4-but(2-)enol,and 1,4-but(2-)inol.

The introduction of alkylene, alkenylene, alkinylene, and aryl units ispreferably done starting from the corresponding halides, especiallychlorides and bromides. Exemplary representatives are1,6-dichlorohexane, 1,4-dichlorobut(2-)ene, 1,4-dichlororbut(2-)ine, and1,4-bis(chloromethyl)benzene.

Polyalkylene oxide units can also be introduced via the α,ω-dihalogencompounds. These are from the oligomeric and polymeric alkylene oxidesof the general compositionHO[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)Hwhere q and r have the meanings specified above, accessible, forexample, by chlorination of the hydroxyl groups with SOCl₂ (Organikum,Oganisch-chemisches Grundpraktikum [Organikum, Basic Practice of OrganicChemistry], 17th edition, VEB Deutscher Verlag der Wissenschaften,Berlin, 1988, pp. 189-190).

Monohydroxyfunctional units, dihydroxyfunctional units, orpolyhydroxyfunctional units can be introduced as the linker V¹ startingfrom epoxide derivatives.

Commercial examples are 1-chloro-2,3-epoxypropane,glycerol-1,3-bis-glycidyl ether, and diethylene glycol diglycidyl ether,and neopentyl glycol diglycidyl ether.

To the extent that they are not available commercially, the desireddiepoxides can, for example, be synthesized by reaction of thecorresponding diols with 1-chloro-2,3-epoxypropane under alkalineconditions.

In the use of epoxides as starting materials for building V¹ it is to benoted that for alkylation of tertiary amino groups one mol H⁺ per moleis to be added per mole epoxide/tertiary amine.

The choice of suitable amines as starting components for building Q alsodetermines to a high degree the molecular structure. The use ofditertiary amines, e.g. N,N,N′,N′-tetramethyl ethylene diamine,N,N,N′,N′-tetramethyl tetraethylene diamine, N,N,N′,N′-tetramethylhexamethylene diamine, N,N′-dimethyl piperazine, leads to products inwhich each nitrogen atom of the repeating unit is quaternized.

The use of secondary-tertiary diamines, e.g. N-methylpiperazine, opensthe way to repeating units -Q-V¹-Q- in which tertiary and quaternaryamine or ammonium structures are present in the ratio 1:1. A partial orcomplete subsequent quaternization of remaining tertiary amino structurerepresents a preferred variant for the setting of a desired high densityof the quaternary ammonium groups. The corresponding aromatic aminesimidazole or pyrazole lead to products with a delocalized charge.

With the use of primary-tertiary diamines (amines with primary andtertiary amine units), for example N,N-dimethyl propylene diamine and1-(3-aminopropyl)imidazole, especially in combination with diepoxides,comb-like structures can be built for which the degree of quaternizationduring a final alkylation is optional. In principle, degrees ofquaternization of, on average, less than one quaternary ammonium groupper repeating unit -Q-V¹-Q- are set. It is, however, preferred toquaternize at least one nitrogen atom per repeating unit Q-V¹-Q-.

Starting from the disecondary amines, e.g. piperazine,N,N′-bis(2-hydroxyethyl)-hexamethylene diamine,N,N′-bis(2-hydroxpropyl)-hexamethylene diamine, repeating units -Q-V¹-Q-can also be synthesized with an average content of less than onequaternary ammonium group. The disecondary amines provide in this casefirst polytertiary aminomodified siloxane copolymers which can bepartially or completely quaternized in a subsequent reaction. It is,however, also preferred in this variant to quaternize at least onenitrogen atom per repeating unit.

Coming into consideration as suitable quaternization agents are thegenerally known groups of substances such as alkyl halides, halogencarboxylic acid ester, epoxide derivatives in the presence of H⁺ anddialkylsulfates, especially dimethyl sulfate.

The production of disecondary amines not available commercially is donein a preferred form of embodiment starting from the correspondingprimary amines, e.g. hexamethylene diamine, by alkylation with epoxidessuch as, for example, ethylene oxide, propylene oxide, orisopropylglycid ether utilizing the different reaction rates of primaryand secondary amines.

Of decisive importance for the synthesis of the compounds according tothe invention are the preparation and the use of cross-liking agents.

The introduction of M^(H)- in D-units to an α,ω-functionalized siloxanechain S is done just as that of branching T-units and Q-units into otherD-units or D′-units or T′-units by acidic equilibration or condensation.It is known: (Silicone, Chemie und Technologie [=Silicones, Chemistryand Technology], Vulkan-Verlag, Essen, 1989, pp. 5, 82-84). By combiningM^(H)-containing structures with D-containing structures, T-containingstructures, or Q-containing structures, the desired terminal or lateral(D′ or T′) reactively functionalized groups S^(v) can be obtained.

An equilibration in the presence of D^(H)-containing structures and, ingiven cases, M^(H)-containing structures provides, SiH-functionalized ina comb-like manner, products which, after appropriate reactivefunctionalization with, for example, unsaturated glycidyl or halogencarboxylic acid ester functions, can serve as cross-linking agentsconsisting of S^(v)—⁽V²⁾—_(>3). The advantage of these siloxane-basedS^(v)—⁽V²⁾—_(>3-) cross-linking agents is the great variability of thestructure which can be adapted to the purpose of use. To be emphasizedhere are the possibilities, on the one hand by the use of alkoxylatedcross-linking structures (V²=polyether groups) to influence thehydrophily of the overall material, and, on the other hand, to increasethe degree of branching by using, for example, butindiole structures.

Preferred reactive cross-linking agents in the sense of S^(v) can bebased on M^(H)-rich structures, for example, on Q(M^(H))₄, T(M^(H))₃,(M^(H))₂T-T(M^(H))₂ (EP 291871). Into this these siloxane-based startingmaterials are catalytically converted with olefinically oracetylenically unsaturated epoxides, e.g. allylglycid ether or halogencarboxylic acid esters, e.g. chloroacetic acid propinylester or thediester of ethylene glycol with undecene carboxylic acid andchloroacetic acid.

Hydrocarbon-based cross-linking agents in the sense of V^(1v) are based,on the one hand, preferably on polyhydroxylated compounds, for example,such as glycerol, trimethylolpropane, pentaerythritol, or sorbitol.These can be esterified easily and in analogy to the already treatedesterification of alkylene oxides with C₂-halogen carboxylic acids toC₄-halogen carboxylic acids, their acid chlorides, or their anhydrides(Organikum, Organisch-chemisches Grundpraktikum [=Organikum, BasicPractice of Organic Chemistry], 17th edition, VEB Deutscher Verlag derWissenschaften, Berlin, 1988, pp. 402-408). Also in these cases it ispossible, through a pre-positioned alkoxylation (V^(1v)=polyethergroups) to increase the hydrophily of the cross linking agent. Thehalogen carboxylic acid esters synthesized in the described manner havedue to the carbonyl activation of the halogen function a particularlyhigh potential for the alkylation of tertiary amino groups.

On the other hand, glycidylfunctionalized cross-linking agents on thebasis of hydrocarbon; are preferred for V^(1v). These are eithercommercially available, such as, for example, triglycidyl derivatives(Aldrich) based on glycerol, or can also be produced by alkalinecatalyzed addition of epichlorohydrine to the desired polyhydroxylatedhydrocarbon. Preferred starting materials are the already mentionedglycerol, trimethylolpropane, pentaerythritol, or sorbitol. Also in thiscase a pre-positioned alkoxylation provides a more hydrophiliccross-linking agent.

The cross-linking agents used in the sense of V^(1v) contain at least 3reactive groups capable of cross-linking, that is, for bonding to Q.

Cross-linking agents in the sense of V², preferably have at least tworeactive structures capable of alkylation. The necessary bonding to thesiloxane chain is done by hydrosylilation via an additional unsaturatedstructure. Suitable, commercially available starting materials arepreferably derivatives of polyhydroxy compounds, for example,monoallylglycerol or monoallyltrimethylol propane. These can bereactively functionalized by esterification with halogen carboxylicacids or esterifications with epichlorohydrine.

Derivatives of this type which are not available commercially areaccessible through two-stage synthesis. First, there is the alkalinecatalyzed monoetherification of the polyhydroxy compound with thecorresponding unsaturated alkenyl halide or alkinyl halide (Organikum,Organisch-chemisches Grundpraktikum [=Organikum, Basic Practice ofOrganic Chemistry], 17th edition, VEB Deutscher Verlag derWissenschaften, Berlin, 1988, pp. 196-199). Subsequently, theintermediate product with halogen carboxylic acids or acid chlorides oranhydrides is esterified. Alternatively, etherification is done withepichlorohydrine under alkaline conditions.

An advantageous variant follows from the use of unsaturated carboxylicacids, their carboxylic acid halides, or anhydrides, e.g. undecenecarboxylic acid, as starting material. First, a monoesterification isdone with the corresponding polyhydroxy compound. Subsequently, theintermediate product is esterified with halogen carboxylic acids or acidchlorides or anhydrides. Alternatively, etherification is done withepichlorohydrine under alkaline conditions.

An additional advantageous variant follows from the use of unsaturateddiols, for example butene diol or butine diol. These can be directlyesterified with halogen carboxylic acids or etherified withepichlorohydrine.

Structural units which correspond to V^(1v)(-Q-), can, for example, bebuilt by the use of polyfunctional amines. On the one hand, it ispreferred to use trifunctional and higher functional primary andsecondary amines. Examples are the Jeffamines of the T-series (HuntsmanCorp.).

Monosecondary ditertiary triamines, for example, N,N,N′,N′-tetramethyldiethylene triamine or N,N,N′,N′-tetramethyl dipropylene triamine arealso suitable. Furthermore, advantageously usable are the commerciallyavailable tritertiary or tetratertiary amines such asN,N,N′,N′,N″-pentamethyl diethylene triamine, N,N,N′,N′,N″-pentamethyldipropylene triamine,N,N-bis-(3-dimethylaminopropyl-)N-isopropanolamine, andtris-(3-dimethylaminopropyl)amine (Huntsman Corp.).

Independently of the choice of the branching structural units, the totalstochiometry, which can be described in essence by Σ(primary+secondary+tertiary N):Σ(linker precursor forming reactivegroups to V²—+reactive groups to V¹)=1:1, is not changed. Cross-linkingagents based on amino groups or other reactive groups replace equivalentamounts of functional groups of structures not capable of cross-linking.

The choice of the branching structural unit essentially decides at whatpoint in time the cross-linking locations in the molecule can beintroduced.

The quaternization reactions are preferably carried out in water, polarorganic solvents, or mixtures of both components. Suitable are, forexample, alcohols, especially methanol, ethanol, i-propanol, andn-butanol, glycols such as ethylene glycol, diethylene glycol,triethylene glycol, and the methyl ethers, ethyl ethers, and butylethers of said glycols. 1,2-propylene glycol and 1,3-propylene glycol,ketones such as acetone and methyl ethyl ketone, esters such as ethylacetate, butyl acetate, and 2-ethyl-hexylacetate, ethers such astetrahydrofuran, and nitro compounds such as nitromethane. The choice ofsolvent is directed essentially toward the solubility of the reactionpartners and the reaction temperature strived for.

The reactions are carried out in the range from 20° C. to 130° C.,preferably 40° C. to 100° C.

The invention relates furthermore to the use of the branchedpolyorganosiloxane polymers in cosmetic formulations, in washing agents,or for surface treatment of substrates.

Along with this the products according to the invention, which, inthemselves, combine the softening properties of siloxane structures andthe tendency of quaternary ammonium groups to combine for adsorption onthe surfaces of negatively charged solid bodies, can be used in cosmeticformulations for skin and hair care, in polishes for the treatment andfinishing of hard surfaces, in formulations for drying automobile, andother, hard surfaces after machine washing, for the finishing oftextiles and textile fibers, particularly permanent hydrophilicsofteners, as separate softeners after the washing of textiles informulations based on anionic/non-ionogenic surfactants for washingtextiles, as well as an aid to ironing and means to prevent or restorecreases in textiles.

The invention furthermore relates to compositions containing at leastone of the branched polyorganosiloxane polymers together with at leastone additional constituent customary for the composition such ascosmetic compositions, washing agent compositions, polishes, shampoos,aids to ironing, or crease-free finishes.

The use of the branched polyorganosiloxane polymers according to theinvention leads in application in the hair cosmetics field to favorableeffects with regard to setting, sheen, hold, body, volume, regulation ofmoisture, color retention, protection against the effects of theenvironment (UV, salt water, etc.), resiliance, antistatic properties,ability to dye, ability to comb, and so on. That means the quaternarypolysiloxane compounds can be used preferentially in cosmetic and haircare formulations according to WO 02-10257.

EXAMPLES Example 1

12.9 g of deionized water, 86.8 g of 2-propanol, 1.02 g (17 mmol) ofacetic acid, 3.4 g (17 mmol) of lauric acid, 2.2 g (25.68 mmol of N) ofN,N,N′,N′-tetramethylhexane diamine, 2.15 g (6.8 mmol of N) of an amineof the composition

with w1+w2=2.5 and v=8.5

and 0.14 g (1.53 mmol of methyl-substituted N) oftris-(3-dimethylaminopropyl)amine are mixed and heated to 50° C. In theclear solution 90.8 g (34 mmol of epoxygroups) of an epoxysiloxane ofaverage composition

are added dropwise and the reaction solution heated for 9 hours at 82°C. After cooling, 197.5 g of a turbid, gray liquid is obtained. Thepolymer contained therein contains the following structural elements

Example 2

12.5 g of deionized water, 87 g of 2-propanol, 1.02 g (17 mmol) ofacetic acid, 3.4 g (17 mmol) of lauric acid, 2.34 g (27.2 mmol of N) ofN,N,N′,N′-tetramethylhexane diamine, 1.67 g (5.28 mmol of N) of an amineof the composition

with w1+w2=2.5 and v=8.5

and 0.63 g (1.53 mmol of N) of a 40% solution of an amine of thecomposition

with w3+w4+w5=5-6

are mixed and heated to 50° C. In the clear solution 90.8 g (34 mmol ofepoxy groups) of an epoxysiloxane of average composition

are added dropwise and the reaction solution heated for 10 hours at 82°C. After cooling, 197 g of a turbid, gray liquid is obtained. Thepolymer contained therein contains the following structural elements

Example 3

3a) 24 g of deionized water, 6 g of concentrated HCl, and 134 g (1 mol)of tetramethyldisiloxane are mixed at room temperature and stirred. In aperiod of time of 20 minutes 88 g (0.33 mol) of tetraethoxysilane areadded to the batch dropwise and the mixture stirred further for 30minutes. After phase separation, 158 g of an oil phase can be taken off.This is dried over 20 g of Na₂SO₄ and subsequently fractionated bydistillation. 71 g of a colorless liquid in the boiling range 79-83°C./16 mmHg are obtained. According to gas chromatography analysis itcontains 89.7% QM^(H) ₄.

3b) 91 g (0.8 mol) of allylglycid ether are presented under nitrogen atroom temperature. After heating to 90° C. 0.15 g of 1% H₂PtCl₆ in2-propanol are first added dropwise and subsequently 50 g (0.52 mol ofSiH) of QM^(H) ₄ are added dropwise. The batch is heated for 3 hours at135° C. Subsequently, all the components volatile up to 150° C./5 mmHgare removed. 107 g of an oily liquid are obtained

3c) 3.5 g of deionized water, 50 g of 2-propanol, 0.27 g (4.47 mmol) ofacetic acid, 0.89 g (4.46 mmol) of lauric acid, 0.615 g (7.14 mmol of N)of N,N,N′,N′-tetramethylhexane diamine, 0,12 g (0.89 mmol) of a 45%aqueous trimethylamine solution, and 0.95 g (0.89 mmol of N) of an amineof the composition

with w1+w2=6 and +v39

are mixed and heated to 50° C. In the clear solution 50 g (4.12 mmol ofepoxy groups) of an epoxysiloxane of average composition

and 0.16 g (0.8 mmol) of the silicon-containing cross-linking agentaccording to 3b are added dropwise and the reaction mixture heated for10 hours at 82° C. 97.7 g of a slightly yellow two-phase liquid areobtained which on cooling becomes highly viscous. The polymer foundtherein contains the following structural elements

Example 4

4a) 238 g (2.24 mmol) of diethylene glycol are presented under nitrogenat room temperature. Under intensive stirring 558 g (4.93 mol) ofchloroacetic acid chloride are added dropwise within one hour. Duringthe dropwise addition the temperature increased to 82° C. and anintensive HCl development sets in. After completion of the dropwiseaddition the batch is heated at 130° C. for 30 minutes. Subsequently allthe components boiling up to 130° C./20 hPa are distilled off. 566 g ofa pale yellow oil of the compositionClCH₂C(O)OCH₂CH₂OCH₂CH₂OC(O)CH₂Clare obtained.The ester's purity determined by gas chromatography is 99.2%.¹³C-NMR:

Substructure shift (ppm) ClCH₂— 40.7 ClCH₂—C(O)— 167.1 ClCH₂—C(O)—OCH₂—65.2 ClCH₂—C(O)—OCH₂ CH₂— 68.64b) 373 g (3.3 mmol) of chloroacetic acid chloride are presented undernitrogen at room temperature. Under intensive stirring 92.1 g (3 mol ofOH) of glycerin are added dropwise within 30 minutes, where the batchtemperature rises from 24° C. to 100° C. There is more stirring for 1hour at 100° C. Subsequently all the components boiling up to 100° C./30mm Hg are removed. 341 g of a clear, yellow-brown, viscous liquid areobtained.

4c) 2.5 g of deioinized water, 10 g of 2-propanol, 4.5 g (22.5 mmol) oflauric acid, and 2.15 g (24.96 mmol of N) of N,N,N′,N′-tetramethylhexanediamine are mixed and heated to 50° C. To the clear solution a mixtureof 37.15 g (11.24 mmol of epoxy groups) of a siloxane of the structure

and 60.53 g (111.24 mmol of epoxy groups) of a siloxane of the structure

and 0.16 g (1.26 mmol of CL) of the diethylene glycol-based esteraccording to 4a) and 0.14 g (1.26 mmol of Cl) of the glycerin-basedester according to 4b) are added. The batch is heated for 6 hours toreflux temperature. After cooling 106 g of a clear amber-coloredsolution are obtained. The polymer found therein contains the followingstructural elements

Example 5 (according to WO 02-010259; not according to the invention).In a 1-liter three neck flask 24 g of water and 4.18 g (48 mmol oftertiary amino groups) of N,N,N′,N′-tetramethyl-1,6-hexane diamine and12.77 g (12 mmol of primary amino groups) of an alkylene oxidederivative available under the trade name Jeffamin® ED 2003 of thestructureH₂NCH(CH₃)CH₂[OCH₂CH(CH₃)]_(a)(OCH₂CH₂)_(38,7)[OCH₂CH(CH₃)]_(b)NH₂with a+b=6are presented at room temperature. Within 5 minutes 12.0 g (30 mmol) ofdodecanic acid in the form of a 50% solution in 2-propanol and 1.8 g (30mmol) of acetic acid are added. After heating of the batch to 50° C.within 30 minutes 194.1 g (60 mmol of epoxy groups) of an epoxysiloxaneof the average composition

and 30 ml of 2-propanol are added dropwise. The yellow, turbid mixtureis heated for 6 hours to reflux temperature. After removing all of thecomponents volatile up to 100° C./2 mmHg in vacuum 209 g of a beige,turbid material of the structure

are obtained.

Example 6

To demonstrate the suitability as a softener 2.2 kg of commerciallyavailable terry cloth hand towels are washed with 45 g of PersilMegaperls® at 95° C. In the 3^(rd) rinse cycle effectively 10 g of thesoftener according to the invention according to Example 1 and 2 as wellas the softener not according to the invention according to Example 5are added in microemulsion. As a reference, a batch of terry cloth handtowels is rinsed without softener. After the rinsing process, the handtowels are divided. One portion is subjected to linen drying while asecond portion is subjected to the program “cabinet drying” in a dryer.

The terry cloth hand towels were evaluated by 6 test subjects where asequence with increasing softness was to be developed. The hardest handtowel was evaluated with 1 point, while the softest hand towel received4 points.

Softener Linen drying Dryer Note Ø Example 1 3.2 3.8 3.5 Example 2 3.62.6 3.1 Example 5 2.2 2.6 2.4 (not inventive) Reference 1 1 1 (withoutsoftener)

It can be recognized that the materials cross-linked according to theinvention according to Examples 1 and 2 were clearly evaluated betterthan the material not according to the invention and not cross-linkedaccording to Example 5.

1. Branched polyorganosiloxane polymer containing at least one group ofthe structure

at least one group of the structure

at least one group of the structure

as well as at least one branching unit which is selected from the groupconsisting of S^(v) and V^(v), where groups V are connected to groups Qand S, groups Q are not connected to groups S the groups S, S^(v), V,V^(v), and Q in a polymer molecule can be the same or different andwhere

wherein R¹ can be the same or different and is selected from the groupconsisting of: C₁ to C₂₂ alkyl, fluoro(C₁-C₁₀)alkyl and C₆-C₁₀ aryl, andn=0 to 1000, S^(v) is a three or higher valent organopolysiloxane unit,Q is a divalent organic group containing at least one ammonium group, Vrepresents a divalent, straight-chain, cyclic or branched, saturated,unsaturated, or aromatic hydrocarbon group with up to 1,000 carbon atomswhich optionally contains one or more groups selected from the groupconsisting of —O—, —NH—, —NR¹—, wherein R¹ is defined as above, —C(O)—,

-and —C(S)—, and which, optionally, is substituted with one or morehydroxyl groups, V^(v) represents a trivalent or higher valent,straight-chain, cyclic or branched, saturated, unsaturated, or aromatichydrocarbon group with up to 1000 carbon atoms which optionally containsone or more groups selected from the group consisting of —O—, —NH—,—NR¹—, wherein R¹ is defined as above,

—C(O)—, and —C(S)—, and which, optionally, is substituted with one ormore hydroxyl groups, and wherein the positive charges resulting fromthe ammonium group are neutralized by organic or inorganic acid anionsand their acid addition salts.
 2. Branched polyorganosiloxane polymeraccording to claim 1, wherein the divalent organic group Q containing atleast one ammonium group is selected from the group consisting of

a quaternized imidazole unit of the structure

a quaternized pyrazole unit of the structure

where R⁵, R⁶, and R⁷ can be the same or different and are selected fromthe group consisting of H, halogen, hydroxyl group, nitro group, cyanogroup, thiol group, carboxyl group, alkyl group, monohydroxyalkyl group,polyhydroxylalkyl group, thioalkyl group, cyanoalkyl group, alkoxygroup, acyl group, acetyloxy group, cycloalkyl group, aryl group,alkylaryl group, and groups of the type—NHR^(W) in which R^(W) means H,alkyl group, monohydroxyalkyl group, polyhydroxyalkyl group, acetylgroup, ureido group, and the groups R⁶ and R⁷ with the carbon atomsbinding them to the imidazole ring, or two of the groups R⁵, R⁶, and R⁷with the carbon atoms binding them to the pyrazole ring, optionally formaromatic five-element to seven-element rings, a diquaternized piperazineunit of the structure

a monoquaternized piperazine unit of the structure

a monoquaternized piperazine unit of the structure

a diquaternized unit of the structure

a monoquaternized unit of the structure

a monoquaternized unit of the structure

a diquaternized unit of the structure

a monoquaternized unit of the structure

a monoquaternized unit of the structure

where t=2 to 10 and R² and R³ =H or represents a monovalent,straight-chain, cyclic or branched, saturated, unsaturated, or aromatichydrocarbon group with up to 40 carbon atoms which optionally containone or more groups selected from the group consisting of —O—, —NH—,—C(O)—, and —C(S)—, and which, optionally, can be substituted with oneor more hydroxyl groups, where R² and R³ can be the same or different,or R² and R³, together with the positively charged nitrogen atom, form afive-element to seven-element heterocycle which, in given cases, canhave in addition one or more nitrogen, oxygen, and/or sulfur atoms, R⁸has the meaning of R², where R⁸ and R² can be the same or different. 3.Branched polyorganosiloxane polymer according to claim 1, wherein

where R¹ is selected from the group consisting of methyl, ethyl,trifluoropropyl, and phenyl, and n is a number from 0 to
 350. 4.Branched polyorganosiloxane polymer according to claim 1, wherein Vrepresents a divalent, straight-chain, cyclic or branched, saturated,unsaturated, or aromatic hydrocarbon group with up to 400 carbon atomswhich optionally contains one or more groups selected from the groupconsisting of —O—, —NH—, —NR¹—, where R¹ is defined as above,

—C(O)—, and —C(S)—, which are optionally substituted with one or morehydroxyl groups.
 5. Branched polyorganosiloxane polymer according toclaim 1, comprising repeating units of the structure

where Q and S are defined as above, V¹ and V² have the meaning of V butare different from one another.
 6. Branched polyorganosiloxane polymeraccording to claim 1, comprising repeating units of the structure

where Q nd S are defined as above, and V¹ and V² have the meaning of Vbut are different from one another.
 7. Branched polyorganosiloxanepolymer according to claim 5 or 6 wherein —V¹— is selected from thegroup, consisting of —R⁹— where R⁹ represents a divalent, saturated orsingly or multiply unsaturated, straight-chain or branched, hydrocarbongroup with two to 25 carbon atoms selected from the group, consisting of—(CH₂)_(u)C(O)O—[(CH₂CH₂O)_(q)—(CH₂CH(CH₃)O)_(r)]—C(O)(CH₂)_(u)——(CH₂)_(u)C(O)O—R⁹—O—C(O)(CH₂)_(u)—, where R⁹ is defined as previously,—(CH₂)_(u)—R¹⁰—(CH₂)_(u)—, where R10 is an aromatic group,—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—CH₂CH₂—,—CH(CH₃)CH₂O[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—CH₂CH(CH₃)— —CH₂CH(OH)CH₂—,—CH₂CH(OH)(CH₂)₂CH(OH)CH₂—, —CH₂CH(OH)CH₂OCH₂CH(OH)CH₂OCH₂CH(OH)CH₂— and—CH₂CH(OH)CH₂O—[CH₂CH₂O]_(q)—[CH₂CH(CH₃)O]_(r)—CH₂CH(OH)CH₂— where u isfrom 1 to 3, q is from 0 to 200, r is from 0 to 200, and q+r>0. 8.Branched polyorganosiloxane polymer according to claim 5 or 6,comprising a group of the structure

where S is defined as above and —V²— is selected from the groupconsisting of:


9. Branched polyorganosiloxane polymer according to claim 1, whereinS^(v) is a trivalent or higher valent organopolysiloxane group which hasat least three silicon atoms which are each connected to three or moregroups V or V^(v) via a bond to a carbon atom of the respective group Vor V^(v).
 10. Branched polyorganosiloxane polymer according to claim 2,comprising a branching group of the formula V^(1v)(—Q—)_(x), whereV^(1v)(—Q—)_(x) is a trivalent or higher valent group, where Q isdefined as above, and x is a whole number of at least three, and whereV^(1v) is selected from the group consisting of:R¹¹—[(CH₂CH₂O)_(v)(CH₂CH(CH₃)O)_(w)—CO—(CH₂)_(u)]₃₋₆—, where R¹¹ is atrivalent or hexavalent group which is derived from a polyol in which 3to 6 hydroxyl-hydrogen atoms are substituted, v and w are numbers from 0to 200, v+w≧0, and u=1 to 3R¹¹—[(CH₂CH₂O)_(v)(CH₂CH(CH₃)O)_(w)—CH₂CH(OH)CH₂]₃₋₆—, where R¹¹, v, andw are defined as above

where t is from 2 to 10 and R² is defined as above

where t is from 2 to 10 and V³ is a partial structure which is derivedfrom V or V^(v), and,

where t is from 2 to 10 and R² and V³ are defined as above.
 11. Branchedpolyorganosiloxane polymer according to claim 10, wherein the polyol isselected from the group consisting of: glycerol, trimethylolpropane,pentaerythritol, sorbitol, and sorbitan.
 12. Branched polyorganosiloxanepolymer according to claim 1, comprising a branching group of thestructure V^(2v) which is connected to at least one group S or S^(v) andwhere V^(2v) is a trivalent or higher valent group which is selectedfrom the group consisting of:—(Z—)_(y)R¹²[—CH₂CH₂O)_(v)(CH₂CH(CH₃)O)_(w)—CO—CH₂)_(u)]_(z)—, where R¹²is a trivalent or hexavalent group which is derived from a polyol inwhich 3 to 6 hydroxyl-hydrogen atoms are substituted, and Z is adivalent hydrocarbon group with up to 20 carbon atoms which optionallycontains one or more groups selected from the group consisting of —O—and —C(O)—, which optionally are substituted with one or more hydroxylgroups, and where the group Z is bonded by one of its carbon atoms to asilicon atom of the groups S or S^(v), v and w are numbers from 0 to200, v+w≧0, u=1 to 3, y=1 to 6, z=0 to 5, z+y=3 to 6,(—)_(m)R¹³[—O(CH₂CH₂O)_(v)(CH₂CH(CH₃)O)_(w)—CO—CH₂)_(u)]_(n)—, where R¹³is a trivalent or hexavalent, saturated or unsaturated, linear, branchedor cyclic hydrocarbon group with up to 10 carbon atoms, (—) represents asingle bond to a silicon atom of the group S or S^(v), v and w arenumbers from 0 to 200, v+w≧0, u=1 to 3, m=1 or 2, n=1 to 5, and m+n=3 to6 (—)_(m)R¹³[—O(CH₂CH₂O)_(v)(CH₂CH(CH₃)O)_(w)—CH₂CH(OH)CH₂]_(n)—, wherem, R¹³, v, w, and n are defined as above,—(Z—)_(y)R¹²[—(CH₂CH₂O)_(v)(CH₂CH(CH₃)O)_(w)—CH₂CH(OH)CH₂]_(z)—, whereZ, y, R¹², v, w, and z are defined as above.
 13. Branchedpolyorganosiloxane polymer according to claim 1, wherein S^(v) and V^(v)are branching units and the molar ratio of the sum of the branchingunits S^(v) and V^(v) to the sum of the linear repeating units S, V, andQ is 0.001% to 20%.
 14. Branched polyorganosiloxane polymer according toone of claims 9 to 13, where the molar ratio of V^(v) to V is from0.002% to 20%.
 15. Branched polyorganosiloxane polymer according toclaim 1, 2, 3, 4, 5, 6, 9, 10, 11, 12, or 13, where the molar ratio ofS^(v) to S is from 0.002% to 20%.
 16. Process for the production of thebranched polyorganosiloxane polymer of claim 1, comprising conversionof: a) at least one organic compound which has two amino groups andwhich optionally comprises a polyorganosiloxane group, with b) at leastone organic compound which has two epoxy groups and which optionallycomprises a polyorganosiloxane group, with c) at least one organiccompound which has two halogen alkylcarbonyloxy groups and whichoptionally comprises a polyorganosiloxane group, as well as d) at leastone branching compound containing at least three functionalitiesselected from the group consisting of amine, epoxy, orchloroalkylcarbonyloxy functional groups. wherein at least one of thecompounds a) to d) contains a polyorganosiloxane group.
 17. A cosmeticformulation, washing agent or formulation for the surface treatment ofsubstrates comprising the branched polyorganosiloxane polymer ofclaim
 1. 18. A shampoo, 2-in-1 shampoo, clear and turbid leave-onconditioner, hair rinse or pearl sheen formulation, setting gel, settingfoam, setting aerosol, or hair-dyeing formulation, comprising thebranched polyorganosiloxane polymer of claim 1.